Nano-TiCl4.SiO2 has been found to be an extremely efficient catalyst for the preparation of 3,4-dihydropyrimidinones/thiones via three-component reactions of an aldehyde, β-ketoester or β-diketone and urea or thiourea under mild conditions. Nano-TiCl4.SiO2 as a solid Lewis acid has been synthesized by reaction of nano-SiO2 and TiCl4. The structural characterization of this acid has been studied by FT-IR (ATR), XRD, SEM and TEM. This process was simple and environmentally benign with high to excellent yields. Furthermore, the catalyst could be recovered conveniently and reused for at least three times.